Reaction product of aldehydes and diazine derivatives



PatentedJuly13,'1943 I I REACTION raopucr or mamas AND nmzmn DERIVATIVES Gaetano F. DAlelio, Pittsfleld, Mass., asslgnor to V General Electric Company, a corporation of New York No Drawing. Application August 5, 1942, Serial No..453,717 j Y zociaims, (01.260-42) This invention relates to the production of-new butylphenyl, etc.) aryl-substituted aliphatic synthetic materials and more particularly to new (e. g., benzyl, phenylethyl, phenylbutyl, phenylreaction products of" particular utility in the p'ropyl, phenylisopropyl, cinnamyl, etc.); and plastics and coating'arts. Specifically the inventheir homologu'e's, as well as-those groups with tion is concerned with compositions of matter one or more of their hydrogen atoms substituted comprising a condensation roduct of ingredients by, for example, a halogen. Specific examples I comprising an aldehyde, including polymeric alof halogeno-substituted,hydrocarbon-radicals are dehydes, hydroxyaldehydes and aldehyde-addi-- chloromethyl,chloroethyl,chlorophenyLdichlomtion products,- e. g., formaldehyde; paraformaldephenyl, chlorocyclohexyl, ethyl chlorophenyl, V hyde, dimethylol urea, trimethylol melamine, alphenyl chloroethyl, br'omoethyl, bromopropyl, dol, glycollic aldehyde, etc-., and a diazine derivfiuorophenyl, iodophenyl, bromotolyl, etc. Preferative corresponding to the following general ablyRin-FormulaIis hydrogen. However, there formula: also maybe used in carrying the present inven- I I tion into efl'ect compounds such, for instance, as

l c I those represented by the general formulas:

v p I ES-C.QHI.-( LNH-E'-NHLO-H:-X' where n represents an integer and is at least 1 J v I I and not morethan 2, Z represents a member of p N I r the class consisting oi oxygen and sulfur, R repreand, more -particularly, sentsa member of the classconsisting ofhydroy m I p (l) -l gen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals, R representsa memberof the (H1N -C- class consisting of divalent hydrocarbon and L J substituted hydrocarbon radicals, more particu- N larly halo-hydrocarbon radicals, and Xrepresents where n, z, R, R. and have the same meanings a h l en atom, more particularly chl rin r as given above with reference toF'ormula I. min fluorin or io in Th se co po n m Illustrative examples of divalent radicals that be named (diamino pyrimidyl thio aliphatic- R in the above formulas may represent are: diamido or aliphatic-thionoamido) (halogezio alivalent aliphatic, e; g., ethylene, propylene (triphatic-amido or aliphatic-thionoamido) derivamethylene), propenylene, butylene, isobutylene, tives of divalent hydrocar ns. pentylene, isopentylene, etc., including divalent h pp i on is a ontin ati n-impart of cycloaliphatic, e. g, cyclopentylene, cyclopenmy op n application Serial No. 432,895, filed tenylene, cyclohexylene, cyclohexenylene, cyclo- February 28, 1942, and assigned to the same asheptylene, etc.; divalent aromatic, e. g.. 'phenylsignee as'the present invention. ene, xenylene,- naphthylene, etc.'; divalent aliustra a p s of o va nt radicals 4o phatic-substituted aromatic, e. g., 2,4-tolylene,. that R. in the above formula may represent are: ethyl 2,5-phenylene, isopropyl 3,4-phenylene, 1- ph i 8-, m h l, YLPI DYL i p p'YL- butyl 2,4-naphthylene, etc.; divalent aromaticbutyl, secondary butyl, isobutyl, butenyl, amyl, substituted aliphatic, e. g., phenylethylene, isoamyl, hexyl, octyl, methallyl, ethallyl, crotyl, phenylpropylene, naphthylisobutylene, xylylene, etc), including cycloaliph'atic (e. g;, cyclopentyl, alpha-( i-tolylene) beta'-butyl, etc.; radicals that yc pen n y lohexyl, cyclohex ny yolo may be classed either as divalent aliphatic-subheptyl, etc.) aryl (e. g., phenyl, diphenyl or xenyl, stituted aromatic or divalent aromatic-substinaphthyl, etc.); aliphatic-substituted aryl (e.- g., tuted aliphatic, e. g., 4, alpha-tolylene, 3, betatolyl, xylyl, ethylphenyl, propylphenyl, isopropylphenyleneethyl, 4, alpha-xylyene, 2, gammaphenyl, allylphenyl, 2butenylphenyl, tertiaryphenyylenebutyl, etc.; and their-homologues. as I well as those divalent radicals with one or more of their hydrogen atoms replaced by a substituent, e. g., halogeno, amino, acetyl, acetoxy, carboalkoxy, alkoxy, aryloxy, hydroxy, alkyl, alkenyl, etc. Specific examples of substituted divalent radicals are chloroethylene, chloropropylene, bromo-butylene, chlorophenylene, 'chlorotolylene, bromophenylene, chloron'aphthylene, bromonaphthylene, bromo 1,4-tolylene, chlorocyclopentylene, chlorocyclopente'nylene, carbomethoxyphenylene, ethoxyphenylene, acetophenylene, acetoxy- Y phenylene, bromocyclopentylene, aminophenylene, phenoxyphenylene, methylphenylene, (tolylene), allylphenylene, etc. Preferably R is ethylene, phenylene or tolylene.

Instead of the diamino [(NHR)2] pyrimidine (1,3-diazine) derivatives representedby the above formulas, corresponding derivatives of the 1,2-diazines or of the 1,4-diazines may be employed;

The diazine derivatives that are used in carrying the present invention into eii'ect are more fully described and are specifically claimed in my above-identified parent copending' application Serial No. 432,895. As pointed out in this copending application, a method of preparing the diazine derivatives used in practicing, the present invention comprises effecting reaction between a bis-(halogeno alipha'tic-amido)-substituted divalent compound, more particularly a divalent hydrocarbon or halo-hydrocarbon, or a bis-(halogeno aliphatic-thionoamido) -substituted divalent compound and a mercapto di'amino [(-NI-IR.):]-

pyrimidine in the presence of a hydrohalide acceptor, e. g., an alkali-metal hydroxide, the reactants being employed in the ratio of one mol of the mercapto diamino pyrimidine per mol of the said substituted divalent compound.

Examples of diazine derivatives embraced byv Formula I that may be employed in producing the new condensation products of the present invention are the (diamino. pyrimidyl thio acetamido) (halogeno acetamido) -substituted aliphatic hydrocarbons, more particularly the (diamino pyrimidyl thio acetamido) (halogeno acetamido) alkanes, e. g., alpha-(4,6-dlamino pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane alpha-(2,4-diamino pyrimidyl-6 thio acetamido) beta-(chloroacetamido) ethane, the alpha-(diamino pyrimidyl thio acetothionoamido) beta- (chloroacetothionoamido) ethanes, the (diamino pyrimidyl thio acetamido) (halogeno acetamido) substituted aromatic hydrocarbons, e. g., the (diamino pyrimidyl thio acetamido) (halogeno acetamido) benzenes, the (diamino pyrimidyl thio acetothionoamido) (halogeno actothionoamldo) benzenes, the (diamino pyrimidyl thio acetamido) (halogeno acetamido) toluenes, etc.

More specific examples of diazine derivatives that may be employed in producing my new condensation products are listed below:

(Diamino pyrimidyl thio acetamido) (chloroacetamido) propanes, including the (4,6-diamino pyrimidyl-2 thio acetamido) (chloroacetamido) propanes and the (2,6-diamino pyrimidyl-4 thio acetamido) (chloroacetamido) propanes (Diamino pyrimidyl thio acetothionoamido) (bromoacetothionoamido) propanes (Diamino pyrimidyl thio acetamido) (chloroacetamido) butenes (Diamino pyrimidyl thio acetamido) (iodoacetamido) pentanes (Diamino pyrimidyl thio acetamido) acetamido) octane (Diamino pyrimidyl thio 'acetamido) (Diamino pyrimidyl thio acetamido) acetamido) chlorobutanes (Diamino pyrimidyl thio acetamido) acetamido) chlorobenzenes (Diamino pyrimidyl thio acetamido) acetamido) toluenes (Diamino pyrimidyl thio acetamido) acetamido) xylenes (Diamino pyrimidyl thio acetamido) acetamido) naphthalenes (Diamino pyrimidyl thio acetamidol acetamido) ethylbenzenes (Diamino pyrimidyl thio acetothionoamido) (chloroacetothionoamido) cyclohexanes (Diamino pyrimidyl thio acetamido) (chloroacetamido) butenes (Diamino pyrimidyl thio acetamido) acetamido) cyclohexenes' (Diamino pyrimidyl thio acetamido) acetamido) bromobenzenes (Diamino pyrimidyl thio acetamido) acetamldo) chloronaphthalenes (chloro- (bromo- (chloro- (chloro (chloro chloro- (bromo- (chloro- (Diamino pyrimidyl thio acetothionoamido) (chloroacetothionoamido) hexanes (chloroacetamido) heptanes -Alpha-(diamino pyrimidyl alpha'-thio propan- (Diamino pyrimidyl beta-thio propanamido) (beta'-chloro propanamido) cyclopentanes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-chloro propanamido) benzenes (Diamino pyrimidyl beta-thio propanamido) (beta-chloro propanamido) benzenes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-chloro propanamido) toluenes (Diamino pyrimidyl beta-thio propanamido) (beta'-bromo propanamido) toluenes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-iodo.propanamido) xylenes (Diamino pyrimidyl beta-thio propanamido) (beta'-chloro propanamido) xylenes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-fluoropropanamido) ethylbenzenes (Diamino pyrimidyl beta-thio propanamido) (beta'-chloro propanamido) naphthalenes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-chloro propanamido) chloronaphthalenes (Diamino pyrimidyl beta-thio propanamido) (beta-bromo propanamido) bromobenzenes (Diamino pyrimidyl alpha-thio propanamido) (alpha'-chloro propanamido) chlorobutanes (chloro- (Diamino pyrimidyl beta-thio propanamido) (beta-chloro propanamido) anthracenes (Diamino pyrimidyl alpha-thio propanthionoamido) (alpha-chloro propanthionoamido) benzenes (Diamino pyrimidyl beta-thio propanthiono amido) (beta'-bromo propanthionoamido) toluenes Alpha-(4,6-di-[methy1amino] -methyl pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane (4-chloroethylamino G-methylamino pyrimidyl-2 beta-thio propanamido) (beta'-iodo propanamido) butanes v (2-isopentylamino 4-chlorophenylamino pyrimidyl-6 thio ethyl xylyl acetamido) (ethyl xylyl chloroacetamido) cyclohexanes (2-cyclohexylamino 4-isobutylamino pyrimidyl-G beta-thio propanamido) (beta-bromo propanamido) benzenes (d-xylidinofi-naphthyl 6-ethylanilino pyrimidyl-2 thio bromocyclopentyl acetamido) (bromocyclopentyl chloro acetamido) naphthalenes 4-(4-benzylamino 5'-benzyl 6'-isopropylanilino pyrimidyl-2' thio cyclohexenyl acetothionoamido) Z-(cyclohexenyl bromo acetothiono- It will be understood, or course; by those skilled in the art that, in those compounds listed above that are generically named, the described substituent groupings may be attached to any two positions of the d valent compound represented by R. inFormula I. It also will be understood that the expression "diamino pyrimidyl includes within its meanlnglboth the 4,6-diamino pyrimi- (an-2 and the 2,6-diamino pyrimidyl-4 (2,4-61- amino pyrimidyl-G) derivatives.

The present invention is based'on my discovery that new and valuable materials of particular utility in the plastics and coating arts can be produced by efiecting reaction between ingredients comprising essentially an aldehyde, including polymeric aldehydes, hydroiwaldehydes and aldehyde-additionproducts, and a diazine derivative of the kind embraced by Formula I, numerous examples of which have been given above and in my above-identified parent copending application Serial No. 432,895.

It has been suggested heretofore that resins be made by condensing an aldehyde with a diamino' pyrimidine having attached to one or both of the remaining carbon atoms of the pyrimidine nucleus a thioether grouping, but such resins .are not entirely satisfactory for use in many applications,

for instance in the production or moldingcompounds having a high plastic flow during molding combined with a rapid cure to an insoluble, iniusible state. Surprisingly it was'found that the heat-curable resinous condensation products of this invention and molding compositions made v3 therefrom show excellent flow characteristics during a short-curing cycle.' This is a property that is particularly desirable in a thermosetting resin and molding compound. The molded articles have a high dielectric strength and excellent resistance to arcing. They have a good surface finish and, ingeneral, are better than the ordinary urea-formaldehyde resins in their resistance to water. The cured resins have a high resistance to heat-and abrasion and, therefore, are especially suitable for use where optimum heatand abrasion-resistanceare properties of primary importance.

In practicing-my invention the initial condensation reaction may be carried out at normal or at elevated temperatures,-at atmospheri subatmospheric or super-atmospheric pressures, and

under neutral, alkaline orv acid conditions. Preterably the reaction between the components is initiated under alkaline conditions.

Any substance yielding an alkaline or an acid aqueous solution may be used in obtaining alkaline or acid conditions for the initial condensation reaction. For example, I may use an alkaline substance such as sodium, potassium or calcium hydroxides, mono-, dior tri-amines, etc.

In some cases it is desirable to cause the initial condensation reaction between the components to take place in the presence or a primary condensation catalyst and a secondary condensation catalyst. The primary catalyst advantageously iseither an aldehyde-non-reactable nitrogen-contaming basic tertiarycompound, e..g., tertiary amines such as trialkyl (e. g., trimethyl, triethyl, etc.) amines, triaryl (e. g., triphenyl, tritolyl etc.) amines, etc., or an aldehyde-reactable nitrogen-containing basic compound, for instance ammonia; primary amines (e. g., ethyl amine, Dropyl amine, etc.) and secondary amines (e. g., dij propyl amine, dibutyl amine, etc). The'secon'd;

ary condensation catalyst, which ordinarily is used in an amount less than th amount of the primary catalyst, advantageously is a fixed alkali. for instance a carbonate, cyanide or hydroxide of an alkali metal (e. g.,sodium', pQtassiumQIithium. etc.)

Illustrative examples of acid condensation catalysts that may be employed are inorganic or or v ganic acids suchas hydrochloric, sulfuric,,phosphoric,; acetic, lactic, acrylic, malonic, etc., or I acid salts such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc. Mixtures of acids, of acid salts or of acids and of acid salts may be employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the diazine derivative may be carried out in the presence of solvents or diluents, fillers, other natural or synthetic resinous bodies, or while admixed with other materials that also can react with'the aldehydie reactant or with the diazine derivative, e. g., (NHzCONI-Iz), thiourea, selenourea, iminourea (guanidine), substituted ureas, thioureas, selenoureas and iminoureas, e. g., urea derivatives such as mentioned in my Patent No. 2,285,418, issued,

June 9', 1942, page 1, column 1, lines 41-49; monocarboxyl c and polycarboxylic acids and polyamides of polycarboxylicacids, e. g., acetamide, halogenated acetamides (e. g., a chlorinated acete amide), maleic monoamide, malonic monoamide, itaconic diamide, succinic diamide, phthal c diamide, the monoamide, diamid and triamide of -tricarballylic acid, etc.; aldehyde-reactable diazines other than the diazine derivatives constituting the primary components of the resins oi the ke'tones, urea allavl phenols and numerous other phenolssuch as mentioned in my Patent No. 2,239,441, issued April 22, 1941; monohydric and polyhydric alcoother purposes. The liquid heat hardenable or potentially heat-hardenable condensation products also may be used directly as casting resins,

while those which are of a gel-like nature in partially condensed state may be dried and granulated to form clear, unfilled heat-convertible resins.

hols, e. g., butyl alcohol, amyl alcohol, isoamyl alcohol, ethylene glycol, glycerine, polyv yl alcohol, etc.; amines, including aromatic amines, e. g., aniline, etc.; and the like.

The modifying reactants may be incorporated with the diazine derivative and the aldehyde by mixing all the reactants and eflecting condensation therebetween or by various permutations of reactants as described, for example, in my Patent No. 2,281,559, issued May 5, 1942, with particular reference to reactions involving a non-haloacylated urea, a halogenated acylatedurea and an aliphatic aldehyde (page 2, column 1, lines 49-69). For instance, I may form a partial condensation product of ingredients comprising (1) urea or melamine or urea and melamine, (2) a diazine derivative of the kind embraced by For- In order that those skilled in the art better may understand how the present invention may be carried into eifect, the following examples are given by way of illustration andnot by way of limitation. All parts are by weight.

Example 1 v P Alpha-(4,6-diamino pyrimidy1-2 thio acetamido) beta-(chloroacetamido) ethane 31.9 Aqueous formaldehyde (approx. 37.1%

HCHO) 65.8

Aqueous were heated together solution of sodium hydoxide 0.5 under reflux at the boiling temperature of the mass for 15 minutes, yielding mula I, for example a (diamino pyrimidyl thio acetamido) (halogeno acetamido) -substitutedali phatic hydrocarbon, more paricularly a (diamino pyrimidyl thio acetamido) (halogeno acetamido) alkane such, for instance, as alpha-(4,6-diamino pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane, alpha-(2,6-diamino pyrimidyl-4 thio acetamido) beta-(chlorocetamido) ethane, etc., a (diamino pyrimidyl thio acetamido) (halogeno acetamido) -substituted aromatic hydrocarbon, e. g., a (diamino py imidyl thio'acetamido) (halogeno acetamido) benzene, a (diamino pyrimidyl thio acetamido) halogeno acetamido) toluene, etc., and (3) an aldehyde, including polymeric aldehydes,hydroxyaldehydes and aldehydeaddition products, for instance formaldehyde, paraformaldehyde, glyceraldehyde, dimethylol 'urea, a polymethylol melamine, e. g., hexamethylol melamine, etc. Thereafter I may effect re action between this partial condensation product and, for example, a curing reactant, specifically a chlorinated acetamide, to obtain a heat-curable,

composition.

Some of the condensation products of this invention are thermoplastic materials even-at an advanced stage of condensation while others are thermosetting or potentially thermos'etting bodies that convert under heat or under heat and pressure to an insoluble, infusible state. The thermoplastic condensation products are of particular value as plasticizers for other synthetic resins. The thermosetting or potentially thermosetting condensation products, alone or mixed with flllers, pigments, dyes, lubricants, plasticizers, curing agents, etc., may be used, for example, in the production of molding compositions.

The liquid intermediate condensation products of this invention may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions of adjusted viscosity and concentrations. The heatconvertible or potentially heat-convertible resinous condensation products may be used in liquid state, for instance as surface-coating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications, in producing laminated articles and for numerous a clear, resinous syrup. This syrup was mixed while hot with'33 parts alpha cellulose in flock form and 0.2 part of a mold lubricant, specifically zinc stearate. The resulting wet molding composition was divided into two equal parts. To one portion was added 1.3 parts chloroacetamide (monochloroacetamide) and the mixture then was ground in a mortar until a homogeneous mass resulted. Both portions of molding compound were now dried at room temperature until suflicient moisture had been removed to provide a material that could :be molded satisfactorily. Samples 01' the dried positions were molded at 140C. under a pressure of 6,750 pounds per square inch. The sample containing the chloroacetamide was molded for 5 minutes and the other sample, for 7 minutes. In both cases well-cured molded pieces having well-knit and homogeneous structures were obtained. Both pieces showed good resistance to water as evidenced by the fact that, when immersed inboiling water for 15 minutes followed by immersion in cold water for 5 minutes, the molded piece made from the chlorocetamide-contalning molding compound absorbed only 4.2% by weight of water while the other molded piece absorbed only 3.9% by weight of water. (When similarly tested for water resistance, molded articles made from the ordinary urea-formaldehyde molding compositions absorb about 5-7 by weight of water.) The molding compounds showed very good plastic flow during molding as indicated by the amount of flash on the molded p ece.

Example 2 Alpha-(4,6-diamino pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane- 31.9 Aqueous formaldehyde (approx. 37.1%

HCHO) 150.0 Aqueous ammonia (approx. 28% NH3)- 0.6 Aqueous solution of sodium hydroxide were placed in a flask which, in turn, was shaken at room temperature for approximately 16 hours. The reaction product was in the form of a clear, light pink solution that was quite viscous. When a sample of this syrupy condensation product was heated on a C. hot plate, it bodied slowly to a flexible, infusible sheet that showed good plastic flow during curing to the fusiblestate.

and ground molding com-.

Parts Example 3 g Parts Alpha-(4,6-diamino pyrimidyl-Z thio aceting temperature of the mass for minutes,

were heated together under reflux at the boilyielding a syrupy intercondensation product that amido) beta-(chloroacetamido) ethane- 31.9

Urea 30.0

Aqueous formaldehyde (approx. 37.1% ECHO) 123.0 'Aqueous ammonia (approx. NE) 3.5

Aqueous solution 0! sodium hydroxide were heated together under reflux at the boiling tdnperature oi the mass for minutes, yielding a clear, resinous syrup. This syrup was mixed with 66 parts alpha cellulose and 0.2 part ainc stearate to form-a molding compound. The wet molding composition was dried at room temperature ior about 16 hours. A well-cured molded piece having good water resistance and a well-knit and homogeneous structure. was obtained by molding a sample oi the dried and bodied to a potentially thermosetting resin when a sample of it was heated on a 140 C. hot plate. Chloroacetaniide, glycine, sulfamic acid, phthalic anhydride and other curing agents such as mentioned under Example 4- accelerated the conversion of the resin to acured or insoluble and iniusible state.

Example 6" Parts Alpha-(4,6-diamino pyrimidy1-2 thio acetamido) .beta-(chloroacetauudo) ethane" 31.9 Melamine 63.0

. Aqueous ammonia (approx. 28%. NHs) ground molding compound for 7 minutes at t 140 (LU-under a pressure or 6,750 pounds per square inch. The molding composition showed. excellent plastic-flow during molding. i

- 1 e i I Same as Example Bwith the exception that the mixedingredientswere heated together under reflux for only 25 minutes. after which 2 parts chloroacetamide were added and refluxing was continued for an additional 5 minutes. The chlogeneous structure was obtained Its water resiltance was somewhat better thancthat of the molded article of Example 3. It absorbed only 2.8%; by weight 01' water when tested for its water resistance as described under Example 1'.-

roacetamideiunctionsasacuringreactant. Awellcured molded piece having awell-knit and home- Instead of using chloroacetamide as above described. heat-convertiblecompositions may beproduced by adding'to the partial condensationx product (in syrupy or other'form) direct or active curing catalysts (e. g., citric acid, phthalic' acetate; I-diethyl chloroacetamide. glycine ethyl tor-hydrochloride, etc), or. by intercondcnsation. with curing reactants otherthan monochloracetamide (e. g.,'diand trl-chloroacetamides. chloroacetonitriles, alpha, beta-.dibromopropionitrile," aminoacetamide hydrochloride,

ethylene diamine monohydrochlorid'e, the ethanolamiue hydrochlorides, nit'rourea. chloroacetyl urea. chloroac'etone, glycine, aulfamlc acid,

,citrlc diamide, phenacyl chloride,,etc.). Other examples of curing reactants that may be-employed to accelerate or to eilect the curing oi! the thermosetting or potentially thermosetting resins oi this and other examples are given in various oopending applications of mine, for instance in copending applications Serial No. 346,962, filed July .23, 19:40, and Serial N0. 354,395; filed August 27, 1940, tom of which applications are asas the present invention.-

Example 5 Parts Urea v 60.0 Alpha-(4,6-diamino pyrimidyl-2 thio acetamide) beta-(chloroacetamido) ethane- 8.0 Aqueous formaldehyde (approx. 37.1%

ECHO) 134.0 Aqueous ammonia (approx. 38.% N113)..- 3.5 us solution of sodium hydroxide 'anhydride, malcnic acid, oxalic acid, etc). or latent curing catalysts (e. g sodium chloroi Alpha-(4.6-diamlno pyr1midyl-2 thio acettaming approx; 11% .by weight of water) 60.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 35.0 Aqueous ammonia (approx. 28% NR1)---" 4. 3 Aqueous solution of sodium hydroxide (0.5 N) v 2. 2 so Chloroacetamide 2.0 Water 45.0

Aqueous formaldehyde (approx. 37.1%:

HCHO) 157.0

Aqueous solution of sodium hydroxide (0.5 N) 3.0 Chlproacetamide 1.8

pounds per square inch. The molded piece was removed hot from the mold and didnot warp or become distorted uponcooling to room temperature. It was well cured throughout and had awell-knit and homogeneous structure. Ithad excellent resistance to water as shown by the fact that it absorbed only 0.65% by weight of water when tested for its water resistance as dese bed under Example 1. pound showed excellent flow during molding as evidenced by the amount of flesh on the molded piece.

I Example 7 Parts amido) beta-(chloroacetamido) ethane-.- Dimethylol urea (commercial grade con-- were heated together under-reflux at the, boiling temperature 01 the mass for 20 minutes. The resuiting resinous syrup' was mixed with parts alpha cellulose and 0.3 part zinc stearate to form a molding compound. The wet molding com'position was dried at room temperature until sufllcient moisture had been removed to provide ematerial that could be molded satisfactorily. A'

well-molded piecev was obtained by molding a sample of the dried and ground molding compound Ior 5 minutes at C. under apressure u of 6,750 pounds per square inch.

The molding com- Alpha-4,6-diamino pyrimidyl-2 thlo acet- Example 8 Parts Alpha-(4,6-diamino pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane 31.9

All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 8 minutes. A molding composition was made from the resulting resinous syrup by mixing therewith 75 parts alpha cellulose, 0.4 part zinc stearate and the above-stated amount of chloroacetamide. The wet molding compound was dried as described under Example 7. A wellcured molded piece was obtained by molding a sample of the dried and ground moldins compound ior minutes at 140 C. underya pressure of 6,750 pounds per square inch. It had a wellknit and homogeneous structure and excellent resistance to water as shown by the fact that it absorbed only 0.46% -by weight of water when tested for its water resistance as described under Examplel. The plastic flow of the molding com-.

pound during molding was very good.

Example 9 amido) beta-(chloroacetamido) ethane 15.9

Acrolein 28. 0

Aqueous solution of sodium hydroxide Water 20.0

Emmple 10 Parts Parts i Alpha-(4,6-diamino pyrimidy1-2 thio aoetamido) beta-(chloroacetamido) ethane..- 15.9 Furi'ural 48.0

Aqueous ammonia (approx. 28% NH:) 1. 0 Aqueous solution of sodium hydroxide were heated together under reflux at the boiling temperature oi the mass for 14 minutes, yielding a dark brown. resinous syrup. This syrup formed a hard, well-cohered, infusible sheet when a sample of it was heated on a 140 C. hot plate. The resinous material of this example may be used in the production of molding compounds or as a modifier oi synthetic resins of inadequate flow characteristics to improve their plasticity.

Example 11 Parts Alpha-(4,6-diamino pyrimidyl-2 thio acetamido) beta- (chloroacetamido) ethane 15. 9 Butyl alcohol 37.0 Aqueous formaldehyde (approx, 37.1%

HCHO) 40.5 Aqueousammonia (approx. 28% NHJ) 1.0

Aqueous solution of sodium hydroxide water-resistant and smooth, and adhered tightly to the glass surface. The solubility and filmforming characteristics of the resinous composition of this example make it especially suitable for use in the preparation of coating and impregnating compositions. For example, it may be used in the production or spiritand-baking varnishes. It may be employed as a modifler oi varnishes oi the aminoplast and alkyd-resin types.

0 Example 12 Partl Alpha-(4,6-diamino pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane-.. ll.

Diethyl malonate Aqueous formaldehyde (approx. 37.1%

HCHO) 81.0

Aqueous ammonia (approx. 28% N113)--- 1. 0

Aqueous solution of sodium hydroxide were heated together under reflux at the boiling temperature of the mass for 15 minutes. yielding a clear, resinous syrup; This syrup bodied to a thermoplastic resin when a sample of it was heated on a C. hot plate.

Example 13 Alpha-(4,8-diamino pyrimidyl-2 thio acetamido) beta-(chloroacetamido) ethane Aoetamide Aqueous formaldehyde (approx. 37.1%

HCHO) 81.0 Aqueous ammonia (approx. 28% NHs) 1.0 Aqueous solution or 'sodiumhydroxide a curing agent.

Example 14 Parts Alpha-(4.6-diamino pyrimidyl-2 thio acetamido) beta(chloroacetamido) ethane" 15.9

were heated together under reflux at the boiling temperature of the mass for minutes, yielding a clear. resinous syrup. This syrup was dehy- 'drated by heating it ona hot plate. .The dehydrated syrup was soluble in dioxane. ethylene glycol, ethylene glycol monoethyl ether, butyl alcohol and other organic solvents. A glass plate was coated with a sample of the dehydrated syrup. The coated plate was baked .for several hours at 70 C. A hard, transparent, waterwhite, water-resistant, smooth, tightly adhering, baked film was formed on the plate. The solu' bility and film-forming characteristics of the resinous composition of this example make it particularly suitable for use in the preparation of coating and impre nating compositions.

Example 15 a Parts Alpha-(4,6 diamino pyrlmidyl-2 thio ace amido) beta-(chloroacetamido) ethane 15.9 Polyvinyl alcohol -2.2 Aqueous formaldehyde (approx. 37.1%

HCHO) 81.0v Aqueous ammonia (approx. 28% NHa) 1.0 Aqueous solution of sodium hydroxide (0.5 .N) a 1.0 Water 20.0

were heated together under reflux at theboiling temperature of the mass'for 10 minutes, yielding a resinous syrup that bodied to a rubbery, semi-infusible state when a sample of it was heated on a 140 C. hot plate in the absence of The addition of chloroacetamide, glycine; 's'uliamic acid or other curing agent such as mentioned under Example 4.to the resinous syrup, followed by heating on a 140 C. hot plate, resulted in the curing of the syrup to an infusible resinous mass, The resinous composition of this example is suitable for use in the production of molding compounds. It also may be used in the preparation of various coating and impregnating compositions.

It will be understood, of course, by those skilled in the art that the reaction between the components may be effected at temperatures ranging, for example, from room temperature to the fusion or boiling temperature of the mixed reactants or of solutions of the mixed reactants,

the reaction proceeding more slowly at normal Y temperatures than at elevated temperatures in accordancewith the general law of chemical reactions. Thus, instead of eifecting reaction between the ingredients of Examples 1 and 3 to 15, inclusive, at boiling temperature as mentioned. in the individual examples, the reaction between the components may be carried out at lower temperatures, for instance at temperatures ranging from room temperature up to the boiling temperature of the mass using longer reaction periods and, in some cases, stronger catalysts and higher-catalyst concentrations.

It also will be understood by those skilled in the art that my invention is not limited to condensation products'obtalned by reaction of ingredienta comprising an aldehyde and the 'speciflc diazine compound named in the above illustrative examples. Thus, instead of alpha (4,6-diamino pyrimidy1-2 thio acetamido) beta- -(chloroacetamido) ethane, I may use, for example, the corresponding fluoro, iodo or bromo derivatives. an alpha-(2,6-diamino pyrimidyl-t thio' acetamido) .beta-(halogeno acetamido) ethane or other-(diamino pyrimidyl; thio'acetamido) (halogeno acetamido) alkane or aikene. a (diamino pyrimidyl thioacetamido) (halogeno acetamido) benzene, toluene or other divalent aromatic hydrocarbon, or any'other diazine derivative (or mixture thereof) of the kind embraced by Formula I, numerous examples of vwhich have been given above and ing application Serial No. 432,895.

In producing these new condensation products the choice of the aldehyde is dependent in my copend [largely upon economic considerations and upon formaldehyde, e. g.,

the particular properties desired in the finished product. I prefer to use as the aldehydic reactant formaldehydeor compounds engendering paraformaldehyde, hexamethylene tetramine, etc. Illustrative examples of other aldehydes that may be used are acetaldehyde, propionaldehyde, methacrolein, crotonaldehyde, octaldehyde, benzaldehyde, furfural, etc., mixtures thereof, or mixtures of formaldehyde (or compounds engendering formaldehyde) with such, aldehydes.

Illustrative examples of aldehyde-addition products thatmay be used instead of the aldehyde: themselves are the monov and poly- (N-carbinol) derivatives, more particularly the monoand poly-methylol derivatives of urea, thiourea, selenourea and imlnourea and of substituted ureas, thioureas,- selenoureas and iminoureas,

monoand poly-(N-carbinol) derivatives oi" amides of poly-carboxylic acids, e. g., male'ic, itaconic, fumaric, adipic', malonic,-succinic, citric, phthalic, etc., monoand poly-(N-carbinol) derivatives of the aminotriazoles, of the aminotriazines, etc. Particularly good results are obtained with active methylene-containing bodies such as a methylol urea, more particularly monoand di-methylol ureas, and a methylol aminotriazine, e. g., monomethylol melamine and polymethylol melamines (di-, tri-, tetra-, pentaand hexa-methylol melamines). Mixtures of aldehydes and aldehyde-addition products may be employed, e. g., mixtures of formaldehydeand methylol compounds such, for instance, "as dimethylol urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio of the aldehydio reactant t the diazine derivative may be varied over a wide range,

but ordinarily the reactants are employed in an amount corresponding to at least one mol of the aldehyde, specifically formaldehyde, for each mol of the diazine derivative. Thus, I may use. for example, from 1 to 7 or 8 or more mols of an aldehyde for each mol of diazine derivative.

Good-results are obtained in manufacturing thermosetting resinous compositions using from about "2 'to 4 mols aldehyde, specifically formaldehyde, for each mol of diazine derivative.

When the aldehyde is available for reaction inthe form of an alkylol derivative, more partic-. ularly a methylol derivative such, for instance, as dimethylol, urea, trimethylol melamine, etc., then higher amounts of such aldehyde-addition products are employed, for instance from 2 or 3 up to 12 or 15 or more mols of such alkylol debutyraldehyde.

6,1942; andothers.

rivatives for each mol of the diazine derivative.

As indicated hereinbefore, and as further shown by a number of the examples, the properties of the fundamental resins of this invention may be varied widely by introducing other modifying bodies before, during or after effecting condensation between the primary components.

Thus, as modifying agents! may use, for instance, monohydric alcohols such as ethyl, propyl isopropyl, isobutyl, hexyl, etc., alcohols, polyhydric alcohols such asdiethylene glycol, triethylene glycol, pentaerythritol, 1etc.;, alcohol- '-ethers, e. g., ethylene glycolmonomethyl. ether, f

assesoo ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene 'glycol, monophenyl .ether, diethylene glycol monomethvlether, di-

ethylene glycol monoethyl ether, diethylene' glycol monobutyl ether, etc.; amides such as formamide,- stearamide, acrylamide; benzene sulfonamides, toluene sulfonamides', adipic diamide,

phthalic dlamide, etc. amines, e. g., ethylene diamine, phenylene diamine, etc.; phenol and-substituted phenols, including aminophenols, etc.: ketones. including halogenated ketones; nitriles,

including halogenated nitriles, e. g.'. acrylonifbe compounded withthe resin-in accordance with are coated and impregnated with the resin, su-

perimposed and thereafter united under heat and pressure. They may be used in theflproduction of wire and baking enamels from which insulated wires and other coated products are made,

for bonding or cementing together mica flakes to form a laminated mica article, for bonding together abrasive grains in the production of resinbonded abrasive articles such,'for instance, as

'grindstones, sandpapers, etc., in the manufacture of electrical resistors, etc. They may be.used

trile, methacrylonitrile, 'succinonitrile, chloroacetonltriles, etc.; acylated ureas, includihg halm" genated acylated ureas of the kind described, for

examplain my Patent No. 2381.359, issued May The modifying boss-ass. a the form of mm molecularweight bodies with or without resinous characteristics, for example, hydrolyzed wood products, formalized cellulose derivatives; t-

lignin, protein-aldehyde condensation products.

aminotriasoie-aldehyde condensation. products,

aminctriasine-aldehyde condensation productazietc; Other examples of modifying bodies are the urea-aldehyde condensation. products, the ani rune-aldehyde condensation products, furi'ural condensation products, phenol-aldehyde conden sation' products, modified or unmodified, saturated'or unsaturatedpolyhydric alcohol-polycar'box- 'ylic acid condensation products, water-soluble "cellulose derivatives, natural gumsand resins such as shellac, etc.; polyvinyl compounds such as polyvinyl esters,- e. 2.. p lyvinyl acetate, polyvinyl butyrate, etc., polyvinyl ethers, includ m polyvinyl acetals, specifically polyvinyl formal, etc.

' Instead of effecting reaction between a diazine derivative of the kind embraced by Formula I and an aldehyde, specifically formaldehyde,

may cause an aldehyde to condense with a (organic or inorganic) of the dlazine derivative or with a mixture of thediazinederivative and a salt thereof. .Examplescf organic and mor ga'nic acids that may be used in the preparation in sheei;

for treating cotton, linen. and other cellulosic v v or other form. 'They alsomay be employed as impregnants for electrical coils and for other electrically insulating applications.

What! claim asnew and-desire to secure by Letters Patent of the United States is:

1-. A composition of matter comprising the product of reaction of ingredients comprising an aldehyde-and a compound corresponding tothe lene'ral formula .& ads

it iri sid s-jean:

(arm

\N represents-an integer-and is at least i and not more than 2, z represents a member of the class consisting of oxygen and sulfur. R represents a member of the class consisting of hy-.- drogen and monovalent hydrocarbon and halo hydrocarbon radicals, R. represents a member of the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen'atom.

2. A composition as in claim 1 wherein the aldehyde is formaldehyde. i

8. A composition as in'olaim 1 wherein the reaction product is an alkaline-catalyzed reaction product of the stated components. I

4. A composition as'in claim '1 wherein R represents a hydrogen atom.

5. A composition as in claim 1 wherein the reaction product is an alcohol-modified reaction product of the stated components.

of such salts are hydrochloric, sulfuric, phos phoric, boric, acetic, chloroacetic, propionic, bu-- so aldehyde and a compound corresponding to the brie, valeric, acrylic, poiyacrylic, oxalic, methacrylic, polymethacrylic, malonic,'succinic, adipic, vmalic, maleic, fumarlc, bensoic, salicylic. phthalic, camphoric, etc.

(BHNJ Dyes, pigments, plasticizers, mold lubricants, I

6. A composition of mattercomprising the product of reaction of ingredients comprising an Ieneral formula -c N H a g -SC.H;. V-NB-R NH c.n..-x

\N/ .I where n represents an integer and is at least 1 and not more than 2, Z represents a member'of the class consisting of oxygen and sulfur, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, R represents a mcmber of the class consisting of divalent hydrocarb'oh and halo-hydrocarbon radicals; and X represents a halogen atom.

7. A heat-curable resinous composition comprising a heat-convertible condensation product of ingredients comprising formaldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, R represents a member of the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

8. A product comprising thecured resinous composition of claim 7.

9. A composition as in claim 7 wherein Z represents oxygen and X represents chlorine.

10. A compositioncomprising a condensation product of ingredients comprising an aldehyde and a (diamino pyrimidylthio acetamido) (halogeno acetamido) -substituted aliphatic hydrocarbon.

11. A composition comprising a condensation product of ingredients comprising an aldehyde where n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, R

represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, R. represents a member of the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

15. A composition as in claim 14 wherein R represents hydrogen, the aldehyde is formaldehyde and the urea component is the compound corresponding to the general formula NH2CONH2.

16. A composition comprising the resinous product of reaction of ingredients comprising urea, formaldehyde and alpha-(4,6-diamino pyrimidyl-Z thio acetamido) beta-(chloro-acetamido) ethane.

1'7. A resinous composition comprising the product of reaction of ingredients comprising dimethylol urea and alpha-(4,6-diamino pyrimidyl-2 thio acetamido) beta-(chloro-acetamido) ethane.

18. A composition of matter comprising the product of reaction of ingredients comprising an aminotriazine, an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting. of oxygen and sulfur, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, R represents a member of the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals, and X rep-' resents a halogen atom.

19. A resinous composition comprising the product of reaction of ingredients comprising melamine, formaldehyde and an alpha-(diamino pyrimidyl thio acetamidol beta-(chloro-acetamido) ethane.

20. The method of preparing new synthetic compositions which comprises effecting reaction between ingredients comprising an aldehyde and a compound corresponding to the general formula is] I where n represents an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals, R represents a member of the class consisting of divalent hydrocarbon and halo-hydrocarbon radicals, and X represents a halogen atom.

GAETANO F. DALELIO.

CERTIFICATE OF CORRECTION Patent No. 2,511,290. "July 15, 1915.

GAETANO F. D'ALELIo.

It is hereby certified that error appears in the printed specification of the ahove numbered patent reqxnringvcorrection as follows: Page 1, second column, line 11.9, for "11., alpha-xylyene' read --11., alpha-xylylene--; line 50, for "phemrylenebutyl read heny'Ienebutylpage 2", first column, line 11.6, after ethene"- insert a comma; and second column, line 28, for beta-alpha' read --beta(alpha' page}, first column, line 57} after "acetamido" insert a closing parenthesis; and secondcolumn, line 66, before "mono-" insert --monoemides of--;. page 11, first column, line 51, for 'paricularly" read --particularly--; line 56, for "(chlor-octamido) read (chloroacetemido) page 11., first column, line 11.1, before "haloge no" insert an opening parenthesis; and second column, line 20, for hydoxide read --hydroxideline 11.8, for "chlorocetamide' read --chloroacetsmide "and line 75, for fusible read -infusible-; page 5, first column, line 11.8-11.9, for the word "monochloracetamide" read --monochloroac etamide--; lin 69-70, for'acetamide read -acetamido--; and second column, line 11.5, for

-"flesh" read "flashpage 6, first column, line 58, for"Alpha-11.,6

diamino' read -A1pha-(l1.,6-d18mino--; page 8, first column, line 9-1C, after "propyl" insert a comma; and second column, line 2-5 for "thermaplastic" read --thermoplastic--'; and that the said Letters Patent shouldb'e read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 21st day of September, A D. 19115.

Henry Van Arsdal e,

(Seal) Acting Commissioner of Patents. 

